US6334904B1 - Water-soluble, water-softening builder - Google Patents

Water-soluble, water-softening builder Download PDF

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Publication number
US6334904B1
US6334904B1 US09/402,786 US40278699A US6334904B1 US 6334904 B1 US6334904 B1 US 6334904B1 US 40278699 A US40278699 A US 40278699A US 6334904 B1 US6334904 B1 US 6334904B1
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US
United States
Prior art keywords
water
tablet
acid
softening
builder
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Expired - Lifetime
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US09/402,786
Inventor
Harald Ahnsorge
Paul Robinson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Reckitt Benckiser Calgon BV
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Reckitt Benckiser NV
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Assigned to BENCKISER N.V. reassignment BENCKISER N.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ROBINSON, PAUL, AHNSORGE, HAROLD
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Publication of US6334904B1 publication Critical patent/US6334904B1/en
Assigned to RECKITT BENCKISER CALGON B.V. reassignment RECKITT BENCKISER CALGON B.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: RECKITT BENCKISER N.V.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/02—Softening water by precipitation of the hardness
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof

Definitions

  • the invention relates to a water-soluble, water-softening builder in the form of a tablet.
  • Tablets have a variety of advantages over powder products: they are easier to dose and handle and can be added more easily to the laundry, they are more compact and permit cost-effective storage.
  • Water softening tablets are sold commercially (Calgon 2-phase tabs) and such tablets are described in EP-A1-0 628 627 (Benckiser), CH-577 937 (Lonza), WO-A1-95/21908 (Henkel) and EP-A2-0 622 449 (Hüls).
  • Water-softening tablets are usually prepared by compressing or compacting water-softening powders. It is, however, difficult to find a balance between the required hardness and abrasion resistance of the tablets and their property of disintegrating and/or dissolving quickly in the wash liquor. Tablets which have been prepared using only a slight compacting pressure tend to crumble and to break up during handling and packaging; tablets which have undergone greater compaction are more durable, but do not disintegrate or disperse in the wash liquor as well either.
  • GB 983243 and GB 989683 disclose detergent tablets having improved dissolution properties, which have been prepared by compaction of spray-dried detergent powders and spraying with water or aqueous sodium silicate solution to reduce the proportion of fine particles.
  • the whole tablet is coated with a film-forming polymer to improve the abrasion resistance.
  • the use of polyacrylic acid is not disclosed.
  • EP-A-0 466 484 discloses detergent tablets comprising compacted particles having a narrow size distribution and uniform and regular particle size. This results in the advantage of an attractive appearance and better disintegration in the wash liquor.
  • EP-A2-0 522 766 discloses detergent tablets comprising compacted particulate detergent compositions in which at least some of the particles have been coated with a material which acts as a binder, but which also promotes disintegration in the wash liquor. Although polymers are claimed as suitable disintegrant additives, polyacrylic acid is not disclosed.
  • EP-A2-0 711 828 discloses a process for the preparation of detergent tablets by compaction of particulate detergent compositions in which a binder is distributed which has a melting point in the range of 35-90° C., where compaction to give tablets takes place at a temperature above 28° C. but below the melting temperature of the binder.
  • Polyacrylates are mentioned as possible binders, but polyacrylic acid is not disclosed.
  • Polymers and copolymers of acrylic acid are known constituents of detergents and water softeners. It has also already been proposed to add alkali metal salts of such polymers or copolymers to tablet formulations.
  • WO-A1-92/18604 discloses a process for the preparation of detergent tablets for dishwashers, where compositions comprising alkali metal polyacrylate are agglomerated and dried in a fluidized bed.
  • WO-A1-93/00419 discloses a process for the preparation of detergent tablets for dishwashers, where a prehydrated mixture of alkali metal polyacrylate and sodium carbonate is prepared, which is then mixed with the other components of the tablet.
  • WO-A1-95/21908 discloses tablets which comprise builders, including layer silicates and which have a reduced water content and are reportedly notable for good solubility in water. Salts of polyacrylates are mentioned here as disintegrants.
  • EP-A1-628 627 discloses a water-soluble, water-softening builder in the form of a tablet consisting of
  • polyacrylic acid can be regarded as a polymer with water-softening properties, the use of polyacrylic acid is not expressly described in this publication.
  • the invention provides improved tablet properties (hardness, strength, abrasion resistance, solvency in the wash liquor) of water-soluble, water-softening builders in the form of a tablet. It has been found that this object can be achieved in tablets which comprise 40-98% by weight of a combination of a) an organic, multifunctional polycarboxylic acid or alkali metal salts thereof, and b) a polymer with water-softening properties, by using polyacrylic acid in acid form as the polymer with water-softening properties.
  • the aim according to the invention is to use a polyacrylic acid having a molecular weight of from 1500 to 8000.
  • the invention thus provides a water-soluble, water-softening builder in the form of a tablet comprising 40-98% by weight of a combination of
  • An organic, multifunctional polycarboxylic acid is taken to mean a polybasic carboxylic acid having additional functional groups, for example hydroxyl groups and/or amino groups.
  • Suitable multifunctional polycarboxylic acids are gluconic acid, tartaric acid and citric acid. Preference is given to citric acid which, like the other acids, can be used in acid form or as an alkali metal salt.
  • polyacrylic acid to be used according to the invention is taken to mean a homopolymer of acrylic acid which still contains free carboxyl groups.
  • this term should also encompass a partially neutralized polyacrylic acid.
  • the polyacrylic acid to be used should have a molecular weight of from 1500 to 8000.
  • a suitable polyacrylic acid which is commercially available, is the product Norasol LMW45D from Norsohaas. This is a partially neutralized polyacrylic acid having a molecular weight of 4500.
  • the builder tablet according to the invention can also comprise further customary additives, in particular it preferably comprises polyethylene glycol, preferably in an amount of 0.5-6% by weight.
  • Suitable polyethylene glycols are those with a relatively high degree of ethoxylation, for example polyethylene glycols having a molecular weight of from 1000 to 6000.
  • the tablets according to the invention can further comprise customary tableting auxiliaries, such as, for example, microcrystalline cellulose and also sodium bicarbonate.
  • Hardness, solubility and abrasion resistance of the tablets are determined by the following methods of measurement:
  • the hardness of the tablets was determined using an Erichsen 486 hardness tester. The device measures the force which is necessary to break one tablet.
  • the solubility of a tablet is measured by immersing it inside a cage with 6 mm wide windows into a beaker containing 1 l of water at room temperature. The tablet is considered to be dissolved when all of the particles have passed through the windows of the cage.
  • the abrasion resistance of a tablet is measured by placing 10 tablets in a rectangular plastic container (170 mm ⁇ 110 mm ⁇ 110 mm) and rotating the container at a rate of 40 revolutions per minute for 1 minute. The amount of powder which is produced in the container is weighed and recorded as a percentage of the original weight of the tablet.
  • the tablets according to the invention produced in this way were compared with tablets produced in the same way which contained the sodium salt of an acrylic acid/maleic acid copolymer (Sokalan CP5 from BASF) or the sodium salt of a partially neutralized acrylic acid/maleic acid copolymer (Sokalan CP45 from BASF) instead of polyacrylic acid.
  • Sokalan CP5 acrylic acid/maleic acid copolymer
  • Sokalan CP45 from BASF

Abstract

The invention provides a water-soluble, water-softening builder in the form of a tablet comprising 40-98% by weight of a combination of
a) one or more organic, multifunctional polycarboxylic acid(s) or alkali metal salts thereof, and
b) a polymer with water-softening properties
in an a:b weight ratio of from 80:20 to 50:50, where the polymer with water-softening properties is a partially neutralized polyacrylic acid having a molecular weight of 1500-8000.

Description

BACKGROUND OF THE INVENTION
The invention relates to a water-soluble, water-softening builder in the form of a tablet.
Water-softening builders in tablet form are widely known. Tablets have a variety of advantages over powder products: they are easier to dose and handle and can be added more easily to the laundry, they are more compact and permit cost-effective storage.
Water softening tablets are sold commercially (Calgon 2-phase tabs) and such tablets are described in EP-A1-0 628 627 (Benckiser), CH-577 937 (Lonza), WO-A1-95/21908 (Henkel) and EP-A2-0 622 449 (Hüls).
Water-softening tablets are usually prepared by compressing or compacting water-softening powders. It is, however, difficult to find a balance between the required hardness and abrasion resistance of the tablets and their property of disintegrating and/or dissolving quickly in the wash liquor. Tablets which have been prepared using only a slight compacting pressure tend to crumble and to break up during handling and packaging; tablets which have undergone greater compaction are more durable, but do not disintegrate or disperse in the wash liquor as well either.
A variety of solutions have already been proposed, particularly for detergent tablets, for improving their physical properties (strength, abrasion resistance and dispersibility).
GB 983243 and GB 989683 (Colgate-Palmolive) disclose detergent tablets having improved dissolution properties, which have been prepared by compaction of spray-dried detergent powders and spraying with water or aqueous sodium silicate solution to reduce the proportion of fine particles. The whole tablet is coated with a film-forming polymer to improve the abrasion resistance. The use of polyacrylic acid is not disclosed.
EP-A-0 466 484 (Unilever) discloses detergent tablets comprising compacted particles having a narrow size distribution and uniform and regular particle size. This results in the advantage of an attractive appearance and better disintegration in the wash liquor.
EP-A2-0 522 766 discloses detergent tablets comprising compacted particulate detergent compositions in which at least some of the particles have been coated with a material which acts as a binder, but which also promotes disintegration in the wash liquor. Although polymers are claimed as suitable disintegrant additives, polyacrylic acid is not disclosed.
EP-A2-0 711 828 (Unilever) discloses a process for the preparation of detergent tablets by compaction of particulate detergent compositions in which a binder is distributed which has a melting point in the range of 35-90° C., where compaction to give tablets takes place at a temperature above 28° C. but below the melting temperature of the binder. Polyacrylates are mentioned as possible binders, but polyacrylic acid is not disclosed.
Polymers and copolymers of acrylic acid are known constituents of detergents and water softeners. It has also already been proposed to add alkali metal salts of such polymers or copolymers to tablet formulations.
WO-A1-92/18604 (Henkel) discloses a process for the preparation of detergent tablets for dishwashers, where compositions comprising alkali metal polyacrylate are agglomerated and dried in a fluidized bed.
WO-A1-93/00419 (Henkel) discloses a process for the preparation of detergent tablets for dishwashers, where a prehydrated mixture of alkali metal polyacrylate and sodium carbonate is prepared, which is then mixed with the other components of the tablet.
WO-A1-95/21908 (Henkel) discloses tablets which comprise builders, including layer silicates and which have a reduced water content and are reportedly notable for good solubility in water. Salts of polyacrylates are mentioned here as disintegrants.
EP-A1-628 627 (Benckiser) discloses a water-soluble, water-softening builder in the form of a tablet consisting of
A) 60-98% by weight of a combination of
a) citrate and/or citric acid and
b) a polymer which acts as a water softener in an a:b weight ratio of from 70:30 to 50:50, preferably from 65:35 to 55:45,
B) 0.5-6% by weight of polyethylene glycol
C) 0-38% by weight of other auxiliaries.
Although polyacrylic acid can be regarded as a polymer with water-softening properties, the use of polyacrylic acid is not expressly described in this publication.
SUMMARY OF THE INVENTION
The invention provides improved tablet properties (hardness, strength, abrasion resistance, solvency in the wash liquor) of water-soluble, water-softening builders in the form of a tablet. It has been found that this object can be achieved in tablets which comprise 40-98% by weight of a combination of a) an organic, multifunctional polycarboxylic acid or alkali metal salts thereof, and b) a polymer with water-softening properties, by using polyacrylic acid in acid form as the polymer with water-softening properties. In particular, the aim according to the invention is to use a polyacrylic acid having a molecular weight of from 1500 to 8000.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention thus provides a water-soluble, water-softening builder in the form of a tablet comprising 40-98% by weight of a combination of
a) one or more organic, multifunctional polycarboxylic acid(s) or alkali metal salts thereof, and
b) a polymer with water-softening properties in an a:b weight ratio of from 80:20 to 50:50, wherein the polymer with water-softening properties is a partially neutralized polyacrylic acid having a molecular weight of 1500-8000.
An organic, multifunctional polycarboxylic acid is taken to mean a polybasic carboxylic acid having additional functional groups, for example hydroxyl groups and/or amino groups. Suitable multifunctional polycarboxylic acids are gluconic acid, tartaric acid and citric acid. Preference is given to citric acid which, like the other acids, can be used in acid form or as an alkali metal salt.
The polyacrylic acid to be used according to the invention is taken to mean a homopolymer of acrylic acid which still contains free carboxyl groups. For the purposes of the invention, this term should also encompass a partially neutralized polyacrylic acid.
The term “partially neutralized” in this connection should, however, in any case exclude neutralization of more than 90% of the free carboxyl groups.
The polyacrylic acid to be used should have a molecular weight of from 1500 to 8000.
A suitable polyacrylic acid, which is commercially available, is the product Norasol LMW45D from Norsohaas. This is a partially neutralized polyacrylic acid having a molecular weight of 4500.
The builder tablet according to the invention can also comprise further customary additives, in particular it preferably comprises polyethylene glycol, preferably in an amount of 0.5-6% by weight. Suitable polyethylene glycols are those with a relatively high degree of ethoxylation, for example polyethylene glycols having a molecular weight of from 1000 to 6000.
The tablets according to the invention can further comprise customary tableting auxiliaries, such as, for example, microcrystalline cellulose and also sodium bicarbonate.
Hardness, solubility and abrasion resistance of the tablets are determined by the following methods of measurement:
The hardness of the tablets was determined using an Erichsen 486 hardness tester. The device measures the force which is necessary to break one tablet.
The solubility of a tablet is measured by immersing it inside a cage with 6 mm wide windows into a beaker containing 1 l of water at room temperature. The tablet is considered to be dissolved when all of the particles have passed through the windows of the cage.
The abrasion resistance of a tablet is measured by placing 10 tablets in a rectangular plastic container (170 mm×110 mm×110 mm) and rotating the container at a rate of 40 revolutions per minute for 1 minute. The amount of powder which is produced in the container is weighed and recorded as a percentage of the original weight of the tablet.
EXAMPLE
50 parts of sodium citrate dihydrate, 19 parts of sodium bicarbonate, 22 parts of Norasol LMW45D (polyacrylic acid), 3 parts of polyethylene glycol (6000) and 6 parts of Avicel (microcrystalline cellulose) were mixed in the dry state, and the resulting granular product was compressed to give tablets in a rotary press at a pressure of 70 KN.
The tablets according to the invention produced in this way were compared with tablets produced in the same way which contained the sodium salt of an acrylic acid/maleic acid copolymer (Sokalan CP5 from BASF) or the sodium salt of a partially neutralized acrylic acid/maleic acid copolymer (Sokalan CP45 from BASF) instead of polyacrylic acid.
The exact compositions of Comparative Examples A and B and the test results with regard to hardness, solubility and brittleness are given in the Table below.
These comparative experiments show that by adding polyacrylic acid in the acid form in accordance with the invention, the hardness of the tablets could be increased and their abrasion resistance could be improved, without impairment of the solubility properties.
TABLE
Comparative Examples Invention
Constituent A(%) B(%) (%)
Citric acid 15 15 —
Na citrate dihydrate 27 27 50
Potassium bicarbonate 27 27 —
Sodium bicarbonate — — 19
Sokalan CP5 gran. ® (1) 11 — —
Sokalan CP45 gran. ® (2) 11 22 —
Norasol LMW45D ® (3) — — 22
PEG6000  3  3  3
Avicel ® (4)  6  6  6
Properties Measurement results
Hardness (N) 110  115  217 
Solubility (s) 60-70 60-70 60-70
Abrasion resistance (%) 16 16  7
(1) gran. acrylic acid/maleic acid copolymer from BASF
(2) gran. Na salt of a partially neutralized acrylic acid/maleic acid copolymer from BASF
(3) polyacrylic acid in acid form, MW 4500, from Norsohaas
(4) microcrystalline cellulose

Claims (5)

What is claimed is:
1. A water-soluble, water-softening builder in the form of a tablet comprising 40-98 % by weight of a combination of
a) at least one organic, multifunctional polycarboxylic acid, or alkali metal salt thereof, and
b) a polymer with water-softening properties in an a:b weight ratio of from 80:20 to 50:50, wherein the polymer with water-softening properties is a partially neutralized polyacrylic acid having a molecular weight of 1500-8000.
2. The builder as claimed in claim 1, wherein the multifunctional polycarboxylic acid is citric acid.
3. The builder as claimed in claim 1, which additionally comprises 0.5-6% by weight of polyethylene glycol.
4. A method of softening water, comprising addition of a builder tablet to water, wherein the tablet comprises 40-98% by weight of a combination of (a) a polyacrylic acid having a molecular weight of 1500 to 8000 and (b) an organic, multifunctional polycarboxylic acid, or alkali metal salt thereof.
5. A method of making a builder tablet, comprising combining a polyacrylic acid having a molecular weight of 1500 to 8000 together with an organic multifunctional polycarboxylic acid or alkali metal salt thereof in a builder tablet wherein the tablet comprises 40 to 98% by weight of said polyacrylic acid and multifunctional polycarboxylic acid.
US09/402,786 1997-04-09 1998-04-03 Water-soluble, water-softening builder Expired - Lifetime US6334904B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19714657A DE19714657C1 (en) 1997-04-09 1997-04-09 Water soluble, water softening builder
DE19714657 1997-04-09
PCT/EP1998/001971 WO1998045400A1 (en) 1997-04-09 1998-04-03 Water-soluble, water-softening builder

Publications (1)

Publication Number Publication Date
US6334904B1 true US6334904B1 (en) 2002-01-01

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US09/402,786 Expired - Lifetime US6334904B1 (en) 1997-04-09 1998-04-03 Water-soluble, water-softening builder

Country Status (7)

Country Link
US (1) US6334904B1 (en)
EP (1) EP0973861B1 (en)
AT (1) ATE205526T1 (en)
CA (1) CA2286158C (en)
DE (2) DE19714657C1 (en)
ES (1) ES2162452T3 (en)
WO (1) WO1998045400A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003083204A1 (en) * 2002-04-03 2003-10-09 Unilever Plc Fabric care composition
US20100249008A1 (en) * 2007-12-10 2010-09-30 Thomas Holderbaum Cleaning Agent
US20100263688A1 (en) * 2009-04-21 2010-10-21 Ecolab Usa Inc. Catalytic water treatment method and apparatus
JP2012214655A (en) * 2011-04-01 2012-11-08 Lion Corp Detergent for dishwasher
US9193610B2 (en) 2011-08-10 2015-11-24 Ecolab USA, Inc. Synergistic interaction of weak cation exchange resin and magnesium oxide

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ZA993473B (en) * 1998-06-17 2000-01-10 Rohm & Haas Pellet formulations.
DE19901064A1 (en) * 1999-01-14 2000-07-20 Henkel Kgaa Aid granules for washing and cleaning active moldings
AU771479B2 (en) * 1999-01-23 2004-03-25 Procter & Gamble Company, The Detergent tablet
US6974789B1 (en) 1999-01-23 2005-12-13 The Procter & Gamble Company Detergent tablet
DE60000022T2 (en) * 1999-03-05 2002-03-14 Rohm & Haas Improved particulate compositions
DE19937428A1 (en) * 1999-08-07 2001-02-08 Henkel Kgaa Detergent tablets
CN102575197B (en) * 2009-09-02 2013-10-30 荷兰联合利华有限公司 Composition and method for treatment of fabric

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US5328633A (en) * 1990-05-04 1994-07-12 The United States Of America As Represented By The Secretary Of The Navy Extended-release plaque preventing and dissolving compositions
DE4318902A1 (en) * 1993-06-07 1994-12-08 Benckiser Gmbh Joh A Water-soluble, water-softening builder
US5618465A (en) * 1991-05-31 1997-04-08 Colgate Palmolive Co. Nonaqueous liquid automatic dishwashing composition containing enzymes
EP0812808A1 (en) * 1996-06-12 1997-12-17 Cleantabs A/S Water softening tablets
US5801137A (en) * 1993-12-23 1998-09-01 The Procter & Gamble Company Detergent compositions containing (poly)carboxylates, organo diphosphonic and acrylic acid derived components, and silicate
US5853430A (en) * 1997-09-03 1998-12-29 The Procter & Gamble Company Method for predissolving detergent compositions
US5858299A (en) * 1993-05-05 1999-01-12 Ecolab, Inc. Process for consolidating particulate solids
US5861366A (en) * 1994-08-31 1999-01-19 Ecolab Inc. Proteolytic enzyme cleaner
US5900399A (en) * 1994-02-10 1999-05-04 Henkel Kommanditgesellschaft Auf Aktien Tablet containing builders

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US5328633A (en) * 1990-05-04 1994-07-12 The United States Of America As Represented By The Secretary Of The Navy Extended-release plaque preventing and dissolving compositions
EP0504091A1 (en) * 1991-03-15 1992-09-16 Cleantabs A/S A phosphate-free automatic dishwashing composition
US5618465A (en) * 1991-05-31 1997-04-08 Colgate Palmolive Co. Nonaqueous liquid automatic dishwashing composition containing enzymes
US5858299A (en) * 1993-05-05 1999-01-12 Ecolab, Inc. Process for consolidating particulate solids
DE4318902A1 (en) * 1993-06-07 1994-12-08 Benckiser Gmbh Joh A Water-soluble, water-softening builder
US5801137A (en) * 1993-12-23 1998-09-01 The Procter & Gamble Company Detergent compositions containing (poly)carboxylates, organo diphosphonic and acrylic acid derived components, and silicate
US5900399A (en) * 1994-02-10 1999-05-04 Henkel Kommanditgesellschaft Auf Aktien Tablet containing builders
US5861366A (en) * 1994-08-31 1999-01-19 Ecolab Inc. Proteolytic enzyme cleaner
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003083204A1 (en) * 2002-04-03 2003-10-09 Unilever Plc Fabric care composition
US20030191044A1 (en) * 2002-04-03 2003-10-09 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Fabric care composition
US7008916B2 (en) 2002-04-03 2006-03-07 Unilever Home & Personal Care Usa Fabric care composition
US20100249008A1 (en) * 2007-12-10 2010-09-30 Thomas Holderbaum Cleaning Agent
US20100263688A1 (en) * 2009-04-21 2010-10-21 Ecolab Usa Inc. Catalytic water treatment method and apparatus
US20100263689A1 (en) * 2009-04-21 2010-10-21 Ecolab Usa Inc. Methods and apparatus for controlling water hardness
JP2012214655A (en) * 2011-04-01 2012-11-08 Lion Corp Detergent for dishwasher
US9193610B2 (en) 2011-08-10 2015-11-24 Ecolab USA, Inc. Synergistic interaction of weak cation exchange resin and magnesium oxide
US9896364B2 (en) 2011-08-10 2018-02-20 Ecolab Usa Inc. Synergistic interaction of weak cation exchange resin and magnesium oxide

Also Published As

Publication number Publication date
EP0973861A1 (en) 2000-01-26
ATE205526T1 (en) 2001-09-15
WO1998045400A1 (en) 1998-10-15
EP0973861B1 (en) 2001-09-12
CA2286158A1 (en) 1998-10-15
ES2162452T3 (en) 2001-12-16
CA2286158C (en) 2007-01-30
DE59801451D1 (en) 2001-10-18
DE19714657C1 (en) 1999-01-07

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